Dietary gel composition



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DIETARY GEL COMPOSITION Herbert Thal Leo and Clarence 'C. Taylor,Anaheim, Calif.

No Drawing. Application January 2, 1957 Serial No. 632,017

Claims. (Cl. 29-132) This invention relates to an artificial sweeteningcomposition and to gels made therefrom. More particularly the inventionrelates to an artificial sweetening composition having substantially nocaloric value and substantially free from sodium compounds, adapted tobe used with a minimum methoxyl pectinic acid in the making ofsugar-free calcium-type gels.

In the preparation of sugar-free calcium-type gels of a dietary naturein accordance with the present invention, We use the minimum methoxylpectinic acid described and claimed in our Patent No. 2,801,178, filedas a continuation-in-part of our now abandoned application Serial No.485,579, filed February 1, 1955. Such a minimum methoxyl pectinic acidis obtained from high methoxyl pectin produced from citrus peel, eitherwith or without isolation of the pectin in a dry, substantially pureform, by the action on such pectin of an enzyme, termed pectase, alsoderived from citrus peel. If the enzymic action is allowed to go tocompletion, as described in the aforesaid application, a minimummethoxyl pectinic acid is obtained that is capable of forming gels,either in the presence or absence of sugar, by an adjustment of the pHof the aqueous solution of such minimum methoxyl pectinic acid to avalue within the range of between 2.75 and 4.50, depending upon thetotal solids content of the aqueous solution or dispersion. In addition,our minimum methoxyl pectinic acid is capable of forming gels withbivalent metals, such as calcium and magnesium, in the absence of sugar,provided the pH is at about 4, and preferably not above about 5.

Our present invention takes advantage of the ability of our minimummethoxyl pectinic acid to form calcium gels and the like in the absenceof sugar, and combines with such minimum methoxyl pectinic acid anartificial sweetening composition capable of providing sufiicientcalcium ions to cause the formation of a calcium jelly even in theabsence of calcium ions from other sources. At the same time, ourartificial sweetening composition imparts to the gel so formed anadequate degree of sweetening, such that no sugar need be used. Thesubstantial absence of sodium from the artificial sweetening compositionmakes it of value in cases where the sodium content of the diet shouldbe as low as possible.

It is therefore an object of the present invention to provide anartificial sweetening composition for use in substantially sodium-freediets and in those diets where sugar should be kept to a minimum becauseof diabetic or lowcalorie requirements.

It is a further important object of this invention to provide acomposition for use in making dietetic gels and the like of low sodiumand sugar content but of good texture and pleasing palatability.

Other and further important objects of this invention will becomeapparent from the following description and appended claims.

In the preparation of our artificial sweetening agent, we employ calciumcyclamate or a mixture of calcium cyclamate and calcium saccharin.Calcium cyclamate is 2,865,761 Patented Dec. 23, 1958 the calcium saltof cyclohexane sulfamic acid, having a molecular weight of about 433 anda calcium content of about 10% by weight. Calcium saccharin is thecalcium salt of 2,3-dihydro-3-oxo-benzisosulfonazole, having a molecularweight of around 516 and a calcium content of about 8% by weight. Thecomposition of our artificial sweetener may be as follows:

Preferred Broad Ranges, Range,

percent percent Calcium Oyclamate 8 or 9 I 5 to 10 Calcium Saccharin 2or 1 5 to 0 In addition to the sweetening compounds,themselves, thecomposition may include about 0.10% of benzoate of soda and 0.005% ofmethyl parabenzoic acid for preservative purposes. For instance, inmaking up one liter of an aqueous solution of the sweeteningcomposition, the preferred proportions are the following:

grams of calcium cyclamate 20 grams of calcium saccharin /2 gram ofmethyl parabenzoic acid 1 gram of benzoateof soda Parts by weightMinimum methoxyl pectinic acid 10 Potassium citrate 8.5 Sodiumhexametaphosphate 6.5 Dextrose 75 'In place of potassium citrate, sodiumcitrate or other alkali metal salt of an edible oXy-organic acid may beused, but potassium, citrate is preferred where a minimum sodium contentin the composition is desired. The potassium citrate serves both as asolubilizing and as a buffer agent for the minimum methoxyl pectinicacid composition. The sodium hexametaphosphate acts as a calciumsequestering agent to eliminate any possibility of gel formation in thestandard aqueous solution of the minimum methoxyl pectinic acid if itwere made up with a hard water, or one containing calcium or magnesium.Other compositions of the aqueous minimum methoxyl pectinic acidsolution may be used in accordance with the disclosures made in theaforesaid pending application.

Our standard liquid pectin is prepared by dissolving 6 oz. grams) of theforegoing minimum methoxyl pectinic acid composition in 36 fluid oz. oftap water to make 40 fluid oz. (1200 cc.) of solution. This solution hasa pH of about 5.10. Two fluid oz. (60 grams) of the standard liquidpectin contain 0.852 gram of minimum methoxyl pectin.

The following example will serve to illustrate a method of preparing asugar-free, acid-type gel, using our standard liquid pectin (minimummethoxyl pectinic acid The following ingredients are mixed together:

1 cup of fruit juice (unsweetened) 2 teaspoonstul of the artificalsweetening solution 1 cup of standard liquid pectin /2 cup of lemonjuice Upon mixing the above listed ingredients, the mass is heated toabout 130 F. to put the ingredients into solution and is then pouredinto a container and cooled to room temperature, whereupon gellingoccurs. The pH is about 3.4, and the gel is an acid-type gel. Since thegel so produced has never been sterilized, it should be i kept in arefrigerator if it is not to be used immediately. The gel has a meltingpoint of about 110 F., and resembles a gelatin type jelly, or dessert. Aone-half /z) cup serving has a value of 40 calories.

The following is an example of a low sugar gel:

Example ll 1 cup of fruit juice (unsweetened) /2 cup sugar 1 cupstandard liquid pectin solution V2 cup lemon juice As before, the aboveingredients are mixed, heated to 130 F., and allowed to cool, whereupongelling occurs. The gel has a pH of about 3.4 and a one-half /2) cupserving has a caloric value of 100. The melting point is above 110 F.

While the gel of Example II contains sugar and is therefore not adiabetic gel, it nevertheless has a sufficiently low sugar content to beuseful in a calorie-controlled diets. From the standpoint of texture andpalatability substantially no difference can be detected between thegels of Examples I and II.

It is also possible to prepare a calcium-type gel merely by the use ofour artificial sweeting composition and our minimum methoxyl pectinicacid solution, without any other ingredients than water. This may betermed a calcium test for our standard liquid pectin, and is carried outby mixing the following ingredients:

Example 111 8 fluid oz. of tap water 1 teaspoonful of our artificialsweeting solution 2 fluid oz. of our standard liquid pectin Q. s lemonjuice to give a pH of about 4.00 (between 3.85

and 4.50)

In the formation of a gel from the ingredients just given in ExampleIII, the amount of calcium supplied by the artificial sweeteningsolution is sufficient to form a calcium gel with our minimum methoxylpectinic acid. One teaspoonful (5 cc.) of the artificial sweeteningsolution is equivalent to about 50 mg. of calcium and that is more thansufficient to elfect the formation of a gel with the amount of minimummethoxyl pectinic acid present, which is equivalent to about 1 gram(0.852 gram) dry weight. Thus, pure water gels of the calcium type canbe prepared from our minimum methoxyl pectinic acid, using ourartificial sweetening solution, even where no calcium is furnished byother ingredients.

In our artificial sweetening solution, made up as described hereinaboveby dissolving 80 grams of calcium cyclamate and grams of calciumsaccharin and making up to 1 liter, the concentration is 10% by weightof the calcium compounds and, hence, the calcium content isapproximately 1% by weight of said solution. Since mg. of calcium issuflicient to form a calcium gel with 1 gram of our minimum methoxylpectinic acid, and since calcium cyclamate contains about 10% by weightof calcium, it follows that 0.5 gram of calcium cyclamate will furnishsufiicien't calcium to effect a gel with from 0.5 to 1 gram of suchpectinic acid furnished by gut standard pectin solution. The gel massmight, then, have the following composition:

300 parts water (supplied by the 8 fluid oz. tap water 2 fluid 02.standard pectin solution) 0.51.00 part minimum methoxyl pectinic acid0.85 part potassium citrate 0.65 part sodium hexametaphosphate 0.05 partsweetening agent Instead of calcium cyclamate alone, the sweeteningcomposition may comprise 8 or 9 parts of calcium cyclamate and 2 or 1parts of calcium saccharin, respectively, without substantially alteringthe amount of calcium furnished by the composition.

Other calcium-type gels can be prepared, with substantially no calories,no sugar and no sodium present, by the use of our artificial sweeteningcomposition, our standard liquid pectin and water packed fruit. Thewater packed fruit is available in 16 oz. cans, or, if sugar isunobjectionable, a fruit packed with sugar may be used. 0ur artificialsweetening composition supplies sufficient calcium ions in oneteaspoonful (5 cc.) to gel one pound of fruit, either water packed orwith sugar, when using cup of our standard liquid pectin. The followingexamples will serve to illustrate this method of preparing calcium-typegels:

Example IV 16 oz. (avoirdupois) of fruit and juice 1 teaspoonful (5 cc.)10% calcium cyclamate solution Mt cup (2 fluid oz.) of our standardliquid pectin The above ingredients are simply stirred together andallowed to set.

Example V 16 oz. (avoirdupois) of fruit and juice 1 teaspoonful of ourartificial sweetener (9% calcium cyclamate-1% calcium saccharin) cup ofour standard liquid pectin Example VI 16 oz. (avoirdupois) of fruit andjuice 1 teaspoonful (5 cc.) of our artificial sweetening com position(8% calcium cyclamate-2% calcium saccharin) A cup (2 fluid oz.) of ourstandard liquid pectin In each of Examples IV through VI, the artificialsweetening composition, whether made up of a 10% solution of calciumcyclamate alone, as in Example IV, or of 9% calcium cyclamate and 1%calcium saccharin, as in Example V, or of 8% calcium cyclamate and 2%calcium saccharin, as in Example VI, furnishes 50 mg. of calcium, andthis is sufiicient calcium to effect a calciumtype gel with 16 oz.(avoirdupois) of fruit and water, in a total mass weighing about 500grams. Using this same ratio, 10 mg. of calcium is capable of effectingthe gelling of grams of an aqueous fruit mass.

The gelling effect of the calcium supplied by our artificial sweeteningcomposition is, of course, controlled by the sodium hexametaphosphatecontent, as a calcium sequestering agent, and the potassium or sodiumcitrate content, as the buffering and solubilizing agent, in ourstandard liquid pectin solution. Using the compositions and proportionsset forth in Examples IV through VI, firm gels, free from syneresis, areproduced, without ever heating the masses above room temperature and atpI-Is of between 3.85 and 4.50 with no sugar present. These gels aresimilar to gelatin jellies in that they can be softened or evenliquified upon the application of heat and will reform or re-set, uponcooling. The temperature at which the gels are reversible is generallyaround F., 50 that they need not be refrigerated except for protectionagainst the gels spoiling due to attack by molds or fungi.

The fact that the sodium hexametaphosphate and the potassium sod ipgzicitrate in the standard liquid pectin controls the action of the calciumfurnished by the artificial sweetening composition is easilydemonstrated. If, instead of using cup of liquid pectin, as in ExamplesIV through VI, A, of a cup of liquid pectin is used, the gel will hardlymold, and if /2 cup of standard liquid pectin is used, the mass remainsa thin fluid or very soft gel. This indicates that there must besufiicient calcium present, as furnished by the artificial sweeteningcomposition, to effect a gel of the minimum methoxyl pectinic acid inthe presence of the sodium hexametaphosphate and potassium or sodiumcitrate, and that this proportion of calcium to minimum methoxyl pectin,to form a calcium-type gel in the absence of sugar, should be about 50mg. of calcium for about 1 gram (0.852 gram) of minimum methoxylpectinic acid, dry weight.

It will be understood that modifications and variations may be efiectedwithout departing from the scope of the novel concepts of the presentinvention.

We claim as our invention:

1. A dietary calcium-type gel composition comprising a minimum methoxylpectinic acid, a sufficient quantity of a substantially sodium-freeartificial sweetening agent selected from the group consisting ofcalcium cyclamate and mixtures of calcium cyclamate and calciumseccharin to furnish at least about 50 mg. of calcium per 1 gram of saidpectinic acid, a sufficient amount of acid and of an alkili metal saltof an edible oxy-organic acid to give the final aqueous gel a pH ofbetween about 3.85 and 4.50 and a suflicient amount of sodiumhexametaphosphate in combination with said oxy-organic acid salt toeffect the dissolution in water of said pectinic acid in the presence ofthe amount of said calcium furnished solely by said sweetening agentwithin the pH range stated when at an elevated temperature butinsufficient to prevent formation of a final aqueous gel at a lowertemperature of set.

2. A dietary gel composition as defined by claim 1, in which theartificial sweetening agent consists of about 4 parts of calciumcyclamate and 1 part of calcium saccharin.

3. A dietary gel composition as defined by claim 1, in which the acidfurnished by lemon juice is citric acid and the alkali metal salt of anedible oxy-organic acid is potassium citrate.

4. A dietary gel composition as defined by claim I, in which theartificial sweetening agent consists of about 4 parts of calciumcyclamate and 1 part of calcium saccharin, the acid furnished by lemonjuice is citric acid, the alkali metal salt of an edible organic acid ispotassium citrate and the amount of water is from 300 to 600 times theweight of said minimum methoxyl pectinic acid in said final aqueous gel.

5. A dietary aqueous gel as defined by claim 4 that is substantiallyfree from sugar and that is in the form of a firm gel, free fromsyneresis and that'has a tem perature of set of about F.

References Cited in the file of this patent UNITED STATES PATENTSHelgren Aug. 20, 1957

1. A DIETARY CHALCIUM-TYPE GEL COMPOSITION COMPRISING A MINIMUM METHOXYLPECTINIC ACID, A SUFFICIENT QUANTITY OF A SUBSTANTIALLY SODIUM-FREEARTIFICAL SWEETENING AGENT SELECTED FROM THE GROUP CONSISTING OF CALCIUMCYCLAMATE AND MIXTURES OF CALCIUM CYCLAMATE AND CALCIUM SECCHARIN TOFURNISH AT LEAST ABOUT 50 MG. OF CALCIUM PER 1 GRAM OF SAID PECTINICACID, A SUFFICIENT AMOUNT OF ACID AND OF AN ALKALI METAL SALT OF ANEDIBLE OXY-ORGANIC ACID TO GIVE THE FINAL AQUEOUS GEL A PH OF BETWEENABOUT 3.85 AND 4.50 AND A SUFFICIENT AMOUNT OF SODIUM HEXAMETHAPHOSPHATEIN COMBINATION WITH SAID OXY-ORGANIC ACID SALT TO EFFECT THE DISSOLUTIONIN WATER OF SAID PECTINIC ACID IN THE PRESENCE OF THE AMOUNT OF SAIDCALCIUM FURNISHED SOLELY BY SAID SWEETENING AGENT WITHIN THE PH RANGESTATED WHEN AT AN ELEVATED TEMPERATURE BUT INSUFFICIENT TO PREVENTFORMATION OF A FINAL AQUEOUS GEL AT A LOWER TEMPERATURE OF SET.